US20230070559A1 - Additive for nonaqueous electrolyte solutions, nonaqueous electrolyte solution containing same, and nonaqueous electrolyte secondary battery - Google Patents

Additive for nonaqueous electrolyte solutions, nonaqueous electrolyte solution containing same, and nonaqueous electrolyte secondary battery Download PDF

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US20230070559A1
US20230070559A1 US17/794,356 US202117794356A US2023070559A1 US 20230070559 A1 US20230070559 A1 US 20230070559A1 US 202117794356 A US202117794356 A US 202117794356A US 2023070559 A1 US2023070559 A1 US 2023070559A1
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nonaqueous electrolyte
group
negative electrode
bis
alkoxysilyl
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Sho Shibata
Hirotetsu Suzuki
Motohiro Sakata
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Panasonic Intellectual Property Management Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an additive for a nonaqueous electrolyte, a nonaqueous electrolyte including the additive, and a nonaqueous electrolyte secondary battery.
  • a material containing a silicon element is promising as a high-capacity negative electrode material for a secondary battery.
  • the material containing a silicon element significantly expands and contracts with charge and discharge, it easily induces side reactions, and the capacity retention rate in charge/discharge cycles tends to be lowered.
  • Non-Patent Literature 1 reports that the capacity retention rate in charge/discharge cycles improves by adding a silane coupling agent containing a vinyl group to an electrolyte of a single electrode battery using a Si/C composite.
  • Non-Patent Literature 1 It is difficult to stably improve capacity retention rate in charge/discharge cycles with the proposal of Non-Patent Literature 1.
  • One aspect of the present disclosure relates to an additive for a nonaqueous electrolyte including an alkoxysilyl compound, wherein the alkoxysilyl compound has two or more silyl groups coupled with an alkylene group or an amino group, the two or more silyl groups each has at least one selected from the group consisting of an alkoxy group and an oxyalkyl group, and the oxyalkyl group is represented by —O—(C x H 2+1 O y ), where x is an integer of 1 or more, and y is an integer of 1 or more.
  • Another aspect of the present disclosure relates to a nonaqueous electrolyte including a nonaqueous solvent, a salt dissolved in the nonaqueous solvent, and the above-described additive for a nonaqueous electrolyte.
  • a nonaqueous electrolyte secondary battery including a negative electrode including a negative electrode mixture layer, a positive electrode, and the above-described nonaqueous electrolyte, wherein the negative electrode mixture layer includes a negative electrode active material, and the negative electrode active material includes a material containing a silicon element.
  • the negative electrode active material contains the material containing a silicon element, capacity retention rate in charge/discharge cycles of a nonaqueous electrolyte secondary battery can be stably improved.
  • FIG. 1 is a partially cut-away plan view schematically illustrating the structure of a nonaqueous electrolyte secondary battery according to an embodiment of the present disclosure.
  • FIG. 2 is a cross sectional view along line X-X of the non-aqueous secondary battery shown in FIG. 1 .
  • FIG. 3 illustrates a production method of a negative electrode for performance evaluation.
  • FIG. 4 is a graph showing relation between the number of charge/discharge cycles and capacity retention rate of a nonaqueous electrolyte secondary battery.
  • the additive for a nonaqueous electrolyte includes an alkoxysilyl compound.
  • the alkoxysilyl compound has two or more silyl groups coupled with an alkylene group or an amino group.
  • Each of the two or more silyl groups has at least one selected from the group consisting of an alkoxy group and an oxyalkyl group, the oxyalkyl group is represented by —O—(C x H 2x+1 O y ), where x is an integer of 1 or more, and y is an integer of 1 or more.
  • the alkoxysilyl compound may be a bis-alkoxysilyl compound or a tris-alkoxysilyl compound.
  • the bis-alkoxysilyl compound the two silyl groups are coupled with an alkylene group or a secondary amino group.
  • the tris-alkoxysilyl compound three alkoxysilyl groups are coupled with a tertiary amino group.
  • the alkoxy group or oxyalkyl group of each silyl group is considered to form X—O—Si bonds with the surfaces of the material containing a silicon element.
  • X denotes the surface of the material containing a silicon element and O coupled with X denotes, for example, an O atom (or residue of OH group) that is present on the surface of the material containing a silicon element.
  • the surface of the material containing a silicon element is covered with a bis-silyl alkane or bis-silyl amine structure (including a tris-silyl amine structure) having stable siloxane bonds at both ends. That is, the surfaces of the material containing a silicon element are covered with a coating (hereinafter, also referred to as SRS coating) containing a bis-silyl alkane or bis-silyl amine structure.
  • SRS coating has a high elasticity, is stable against reversible elastic deformation, and is not easily damaged even when charge/discharge cycle is repeated. As a result, side reaction in the negative electrode is suppressed, and capacity retention rate in charge/discharge cycles is stably improved.
  • the alkoxysilyl compound may be at least one selected from the group consisting of bis(alkoxysilyl)alkane and bis(alkoxysilyl alkyl)amine represented by general formula (1) below:
  • the bis(alkoxysilyl alkyl)amine has an alkylene group between N and Si.
  • R1 is an alkylene group, or a secondary or tertiary amino group. At least one of R2 to R4 is at least one selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, and an oxyalkyl group represented by —O—(C x H 2x+1 O y ), where x1 is an integer of 1 or more, and y1 is an integer of 1 or more.
  • At least one of R5 to R7 is at least one selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, and an oxyalkyl group represented by —O—(C x2 H 2x2+1 O y2 ), where x2 is an integer of 1 or more, and y2 is an integer of 1 or more.
  • the remainder of R2 to R7 is each independently an alkyl group or oxyalkyl group represented by C x3 H 2x3+1 O y3 , where x3 is an integer of 1 or more, y3 is an integer of 0 or more.
  • the oxyalkyl group is a group other than the alkoxy group.
  • the alkoxy group or oxyalkyl group included in R2 to R4 and R5 to R7 each forms a X—O—Si—R1 bond with the surface of the material containing a silicon element, and the surface of the material containing a silicon element is covered with a Si—R1—Si structure having stable siloxane bonds at both ends. That is, the surface of the material containing a silicon element is covered with an SRS coating containing a Si-R1-Si structure.
  • the alkylene group constituting R1 with a larger carbon number allows for better flexibility, which facilitates reversible deformation of the SRS coating.
  • the carbon number of R1 is excessively large, the alkylene chain becomes excessively long, the denseness of the SRS coating is reduced, and the effect of suppressing side reactions is reduced. Therefore, it is desirable that the carbon number of the alkylene group is 1 to 6, and the carbon number of 2 to 4 is more desirable.
  • the bis(alkoxysilyl)alkane is desirably bis(alkoxysilyl)C 1-6 alkane, or may be bis(alkoxysilyl)C 2-4 alkane.
  • R1 may have a structure represented by R11-N—R12.
  • R11 and R12 are each independently an alkylene group with 1 or more carbon atoms. It is considered that such R1 is excellent in flexibility, has significant electron-shielding properties, and is more effective in suppressing side reactions.
  • the amino group with a larger carbon number allows for better flexibility, which facilitates reversible deformation of the SRS coating.
  • the carbon number of the amino group is excessively large, R1 becomes excessively long, the denseness of the SRS coating is reduced, and the effect of suppressing side reactions is reduced. Therefore, it is desirable that the carbon number of the alkylene group is 1 to 6, and the carbon number of 2 to 4 is more desirable.
  • bis(alkoxysilyl alkyl)amine is desirably bis(alkoxysilyl C 1-6 alkyl)amine, or may be bis(alkoxysilyl C 2-4 alkyl)amine.
  • At least one of R2 to R4 may be at least one selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, and an oxyalkyl group represented by —O—(C x1 H 2x+1 O y1 ), where x1 is an integer of 1 to 6, and y1 is 1 or 2; and at least one of R5 to R7 is at least one selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, and an oxyalkyl group represented by —O—(C x2 H 2x2+1 O y2 ), where x2 is an integer of 1 to 6, and y2 is 1 or 2.
  • the alkoxy group and oxyalkyl group may be smaller in view of increasing reactivity with the surfaces of the material containing a silicon element, and the carbon number of the alkoxy group and oxyalkyl group may be, for example, 1 to 3.
  • R2 to R7 is each independently an alkyl group, or an oxyalkyl group other than the alkoxy group represented by C x3 H 2x3+1 O y3 , where x3 is an integer of 1 or more, and y3 is an integer of 0 or more (e.g., integer of 0 or more and 2 or less).
  • the carbon number of the group represented by C x3 H 2x3+1 O y3 may be 1 to 6, or may be 1 to 3.
  • Each of R2 to R4 is independent, and R2 to R4 may each have the same or a different carbon number, or two of R2 to R4 may have the same carbon number.
  • each of R5 to R7 is independent, and R5 to R7 may each have the same or a different carbon number, or two of R5 to R7 may have the same carbon number.
  • two alkoxysilyl groups (R2R3R4Si—, or R5R6R7Si—) coupled with R1 may be the same or different from each other.
  • the two alkoxysilyl groups coupled with R1 may be the same structure.
  • the alkoxysilyl compound when R1 is an alkylene group, is a type of bis(alkoxysilyl)alkane.
  • the SRS coating formed when bis(alkoxysilyl)alkane) is used is composed of a stable siloxane structure and an alkylene structure. Such an SRS coating is not only easy to elastically deform but also chemically and structurally stable.
  • bis(alkoxysilyl)alkane readily available examples include at least one selected from the group consisting of 1,2-bis(trialkoxysilyl)ethane and 1,6-bis(trialkoxysilyl)hexane.
  • 1,2-bis(trialkoxysilyl)ethane include 1,2-bis(trimethoxysilyl)ethane, and 1,2-bis(triethoxysilyl)ethane.
  • 1,6-bis(trialkoxysilyl)hexane include 1,6-bis(trimethoxysilyl)hexane, and 1,6-bis(triethoxysilyl)hexane.
  • the alkoxysilyl compound when R1 is an amino group, is a type of alkoxysilyl alkylamine. More specifically, the alkoxysilyl alkylamine may be at least one selected from the group consisting of bis(alkoxysilyl alkyl)amine and tris(alkoxysilyl alkyl)amine.
  • bis or tris(alkoxysilyl alkyl)amine readily available examples include at least one selected from the group consisting of bis[3-(trialkoxysilyl)propyl] amine and tris[3-(trialkoxysilyl)propyl] amine.
  • examples of the bis[3-(trialkoxysilyl)propyl] amine include bis[3-(trimethoxysilyl)propyl] amine, and bis[3-(triethoxy silyl)propyl] amine.
  • tris[3-(trialkoxysilyl)propyl] amine examples include tris[3-(trimethoxysilyl)propyl] amine, and tris[3-(triethoxy silyl)propyl] amine.
  • the nonaqueous electrolyte includes a nonaqueous solvent, a salt (solute) dissolved in the nonaqueous solvent, and the above-described additive for a nonaqueous electrolyte.
  • the salt (solute) is an electrolyte salt whose ions dissociate in the nonaqueous solvent.
  • the salt includes at least a lithium salt.
  • the component of the nonaqueous electrolyte other than the nonaqueous solvent and salt is an additive, and at least a part of the additive is the above-described alkoxysilyl compound.
  • the concentration of the alkoxysilyl compound in the nonaqueous electrolyte may be, for example, 10 mass % or less, may be 8 mass % or less, or may be 5 mass % or less. The concentration in this range is sufficient for forming a good and suitable SRS coating, regardless of the amount of the material containing a silicon element contained in the negative electrode active material.
  • concentration of the alkoxysilyl compound represented by the formula (1) in the nonaqueous electrolyte of, for example, 0.2 mass % or more, it is considered that a considerable SRS coating is formed, and a significant effect of improving capacity retention rate in charge/discharge cycles of a nonaqueous electrolyte secondary battery can be obtained.
  • the alkoxysilyl compound reacts in the nonaqueous electrolyte secondary battery, the concentration in the nonaqueous electrolyte gradually decreases. Therefore, it is sufficient that the alkoxysilyl compound of the detection-limit or more remains in the nonaqueous electrolyte taken-out from disassembled batteries of those completed nonaqueous electrolyte secondary batteries or nonaqueous electrolyte secondary batteries distributed on the market.
  • cyclic carbonate for example, cyclic carbonate, chain carbonate, cyclic carboxylate, chain carboxylate, etc.
  • examples of the cyclic carbonate include propylene carbonate (PC), ethylene carbonate (EC), and vinylene carbonate (VC).
  • examples of the chain carbonate include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC).
  • examples of the cyclic carboxylate include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • chain carboxylate examples include methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP), ethyl propionate (EP), and the like.
  • a kind of nonaqueous solvent may be used singly, or two or more kinds thereof may be used in combination.
  • the chain carboxylate is suitable for preparation of a low viscosity nonaqueous electrolyte.
  • the nonaqueous electrolyte may include 1 mass % or more and 90 mass % or less of the chain carboxylate.
  • methyl acetate has a particularly low viscosity. Therefore, 90 mass % or more of the chain carboxylate may be methyl acetate.
  • nonaqueous solvent examples include cyclic ethers, chain ethers, nitriles such as acetonitrile, and amides such as dimethylformamide.
  • cyclic ether examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyl tetrahydrofiunn, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4-dioxane, 1,3,5-trioxane, furan, 2-methyl-fiuran, 1,8-cineol, and crown ether.
  • chain ether examples include 1,2-dimethoxyethane, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxy benzene, 1,2-diethoxyethane, 1,2-dibutoxy ethane, diethylene glycol dimethylether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 1,1-dimethoxy methane, 1,1-diethoxy ethane, triethylene glycol dimethylether, tetraethylene glycol dimethylether,
  • These solvents may be a fluorinated solvent in which part of the hydrogen atoms is substituted with a fluorine atom.
  • Fluoro ethylene carbonate (FEC) may be used as the fluorinated solvent.
  • lithium salt examples include, a lithium salt of chlorine containing acid (LiClO 4 , LiAlCl 4 , LiB 10 Cl 10 , etc.), a lithium salt of fluorine containing acid (LiPF 6 , LiPF 2 O 2 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , etc.), a lithium salt of fluorine containing acid imide (LiN(FSO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , LiN(CF 3 SO 2 )(C 4 F 9 SO 2 ), LiN (C 2 F 5 SO 2 ) 2 , etc.), a lithium halide (LiCl, LiBr, LiI etc.) and the like.
  • a kind of lithium salt may be used singly, or two or more kinds thereof may be used in combination.
  • the concentration of the lithium salt in the nonaqueous electrolyte may be 0.5 mol/liter or more and 2 mol/liter or less, or may be 1 mol/liter or more and 1.5 mol/liter or less. By controlling the concentration of lithium salt to be in the above-described range, a nonaqueous electrolyte having excellent ion conductivity and low viscosity can be obtained.
  • Examples of the additive other than the alkoxysilyl compound include 1,3-propanesultone, methylbenzenesulfonate, cyclohexylbenzene, biphenyl, diphenyl ether, and fluorobenzene.
  • a nonaqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and the nonaqueous electrolyte described above.
  • the negative electrode includes, for example, a negative electrode current collector, and a negative electrode mixture layer formed on the surface of the negative electrode current collector.
  • the negative electrode mixture layer contains a negative electrode active material as an essential component, and may contain a binder, a conductive agent, a thickener, and the like as an optional component. Known materials can be used for the optional component such as the binder, the conductive material, and the thickener.
  • the negative electrode mixture layer can be formed, for example, by applying a negative electrode slurry, in which a negative electrode mixture containing a negative electrode active material and a predetermined optional component are dispersed in a dispersion medium, on a surface of the negative electrode current collector and drying.
  • the dried coating film may be rolled, if necessary.
  • the negative electrode mixture layer may be formed on one surface of the negative electrode current collector, or on both surfaces thereof.
  • the negative electrode active material includes a material containing a silicon element.
  • the material containing a silicon element may be treated as a type of alloy based materials.
  • the alloy based material refers to a material containing an element capable of forming an alloy with lithium.
  • Silicon and tin are examples of the element that can form an alloy with lithium, and silicon (Si) is particularly promising.
  • the material containing silicon As the material containing silicon, a silicon alloy, a silicon compound, or the like may be used, and a composite material may also be used. Among them, a composite material containing a lithium ion conductive phase and silicon particles dispersed in the lithium ion conductive phase is promising.
  • the lithium ion conductive phase for example, a silicon oxide phase, silicate phase, carbon phase, or the like can be used.
  • the silicon oxide phase has a relatively large irreversible capacity.
  • the silicate phase is preferable in that its irreversible capacity is small.
  • the main component (e.g., 95 to 100 mass %) of the silicon oxide phase may be silicon dioxide.
  • the composition of the composite material including the silicon oxide phase and silicon particles dispersed therein, as a whole, can be expressed as SiO x .
  • SiO x has a structure in which fine particles of silicon are dispersed in SiO 2 in an amorphous form.
  • the content ratio x of oxygen to silicon is, for example, 0.5 ⁇ x ⁇ 2.0, more preferably 0.8 ⁇ x ⁇ 1.5.
  • the silicate phase may include, for example, at least one selected from the group consisting of Group 1 element and Group 2 element of the long-form periodic table.
  • Examples of the Group 1 element and Group 2 element of the long-form periodic table include lithium (Li), potassium (K), sodium (Na), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and the like.
  • Other elements that can be included are aluminum (Al), boron (B), lanthanum (La), phosphorus (P), zirconium (Zr), titanium (Ti), and the like.
  • the silicate phase containing lithium (hereinafter also referred to as lithium silicate phase) is preferable because of its small irreversible capacity and high initial charge/discharge efficiency.
  • the lithium silicate phase may be any oxide phase containing lithium(Li), silicon (Si), and oxygen (O), and may include other element.
  • the atomic ratio of O to Si in the lithium silicate phase: O/Si is, for example, larger than 2 and less than 4.
  • O/Si is larger than 2 and less than 3.
  • the atomic ratio of Li to Si in the silicate phase: Li/Si is, for example, larger than 0 and less than 4.
  • the lithium silicate phase may have a composition represented by the formula: Li 2z SiO 2+z (0 ⁇ z ⁇ 2).
  • Examples of the elements other than Li, Si, and O included in the lithium silicate phase include iron (Fe), chromium(Cr), nickel (Ni), manganese (Mn), copper (Cu), molybdenum (Mo), zinc (Zn), aluminum (Al), etc.
  • the carbon phase may be composed of, for example, an amorphous carbon with less crystallinity.
  • the amorphous carbon may be, for example, hard carbon, soft carbon, or something else.
  • the negative electrode active material may include a material that electrochemically stores and releases lithium ions, lithium metal, lithium alloy, and the like.
  • a carbon material is preferable.
  • Examples of the carbon material include graphite, soft carbon, hard carbon, and the like. Particularly, graphite with excellent charge/discharge stability and low irreversible capacity is preferable.
  • the negative electrode current collector for example, a metal sheet or metal foil is used.
  • a metal sheet or metal foil is used as the material of the negative electrode current collector.
  • stainless steel, nickel, nickel alloy, copper, copper alloy, and the like can be exemplified.
  • the positive electrode includes, for example, a positive electrode current collector, and a positive electrode mixture layer formed on the surface of the positive electrode current collector.
  • the positive electrode mixture layer contains a positive electrode active material as an essential component, and may contain a binder, a conductive agent, a thickener, and the like as an optional component. Known materials can be used for the optional component such as the binder, the conductive material, and the thickener.
  • the positive electrode mixture layer can be formed, for example, by applying a positive electrode slurry, in which a positive electrode mixture containing a positive electrode active material and a predetermined optional component are dispersed in a dispersion medium on a surface of the positive electrode current collector and drying.
  • the dried coating film may be rolled, if necessary.
  • the positive electrode mixture layer may be formed on one surface of the positive electrode current collector, or may be formed on both surfaces thereof.
  • the positive electrode active material includes, for example, a lithium-containing composite oxide.
  • the lithium-containing composite oxide is not particularly limited, but one having a layered rock salt type crystal structure containing lithium and transition metal is promising.
  • the lithium-containing composite oxide may be, for example, Li a Ni 1 ⁇ x ⁇ y Co x M y O 2 (where 0 ⁇ a ⁇ 1.2, 0 ⁇ x ⁇ 0.1, 0 ⁇ y ⁇ 0.1, 0 ⁇ x+y ⁇ 0.1, and M is at least one selected from the group consisting of Na, Mg, Sc, Y, Mn, Fe, Cu, Zn, Al, Cr, Pb, Sb, and B).
  • Al may be contained as M.
  • the value “a” indicating the molar ratio of lithium is increased or decreased by charging and discharging.
  • Specific examples include LiNi 0.9 Co 0.05 Al 0.05 O 2 , LiNi 0.91 Co 0.06 Al 0.03 O 2 , and the like.
  • the positive electrode active material usually is in the form of secondary particles of coagulated primary particles.
  • the avenge particle size of the positive electrode active material may be, for example, 2 ⁇ m or more, and 20 ⁇ m or less.
  • the average particle size refers to a median diameter in which the cumulative volume in volume-based particle size distribution is 50%.
  • the volume-based particle size distribution can be measured by laser diffraction particle size distribution analyzer.
  • the positive electrode current collector for example, a metal sheet or metal foil is used.
  • a metal sheet or metal foil is used.
  • stainless steel, aluminum, aluminum alloy, titanium, and the like can be exemplified.
  • Examples of the conductive material used for the positive electrode mixture layer and negative electrode mixture layer include carbon materials such as carbon black (CB), acetylene black (AB), Ketjen Black (KB), carbon nanotube (CNT), and graphite.
  • a kind of the conductive material may be used singly, or two or more kinds may be used in combination.
  • binder for the positive electrode mixture layer and negative electrode mixture layer examples include fluororesin (polytetrafluoroethylene, polyvinylidene fluoride, etc., polyacrylonitrile (PAN), polyimide resin, acrylic resin, polyolefin resin, and the like.
  • fluororesin polytetrafluoroethylene, polyvinylidene fluoride, etc.
  • PAN polyacrylonitrile
  • a kind of the binder may be used singly, or two or more kinds may be used in combination.
  • a separator is interposed between the positive electrode and the negative electrode.
  • the separator has excellent ion permeability and suitable mechanical strength and electrically insulating properties.
  • the separator may be, for example, a microporous thin film, a woven fabric, or a nonwoven fabric.
  • the separator is preferably made of, for example, polyolefin, such as polypropylene and polyethylene.
  • an electrode group and a nonaqueous electrolyte are accommodated in an outer package, the electrode group having a positive electrode and a negative electrode wound with a separator.
  • the wound electrode group other forms of electrode group may be applied, such as a laminated electrode group in which a positive electrode and negative electrode are laminated with a separator interposed.
  • the nonaqueous electrolyte secondary battery may be in any form, e.g., cylindrical, prismatic, coin-shaped, button shaped, sheet (laminate) shaped, etc.
  • FIG. 1 is a partially cut-away plan view schematically showing an exemplary nonaqueous electrolyte secondary battery structure.
  • FIG. 2 is a cross sectional view along line X-X in FIG. 1 .
  • a nonaqueous electrolyte secondary battery 100 is a sheet type battery, and includes an electrode group 4 and an outer case 5 for accommodating the electrode group 4.
  • the electrode group 4 has a structure in which a positive electrode 10 , a separator 30 , and a negative electrode 20 are stacked in this order, and the positive electrode 10 and the negative electrode 20 face each other with the separator 30 interposed therebetween.
  • the electrode group 4 is formed in this manner.
  • the electrode group 4 is impregnated with a nonaqueous electrolyte.
  • the positive electrode 10 includes a positive electrode active material layer 1 a and a positive electrode current collector 1 b .
  • the positive electrode active material layer 1 a is formed on the surface of the positive electrode current collector 1 b.
  • the negative electrode 20 includes a negative electrode mixture layer 2 a and a negative electrode current collector 2 b .
  • the negative electrode mixture layer 2 a is formed on the surface of the negative electrode current collector 2 b.
  • a negative electrode tab lead 1 c is connected to the negative electrode current collector 1 b
  • a negative electrode tab lead 2 c is connected to the negative electrode current collector 2 b
  • the positive electrode tab lead 1 c and negative electrode tab lead 2 c each extends out of the outer case 5 .
  • An insulating tab film 6 insulates the positive electrode tab lead 1 c from the outer case 5 , and the negative electrode tab lead 2 c from the outer case 5 .
  • a coating film was formed by applying the negative electrode slurry on one side of a negative electrode current collector (electrolytic copper foil). After the coating film was dried, the coating film was rolled together with the negative electrode current collector by a roller to obtain a negative electrode including a negative electrode mixture layer.
  • a negative electrode was cut into the form shown in FIG. 3 ( a ) and a negative electrode 20 for evaluation was obtained.
  • the region of 60 mm ⁇ 40 mm is a region to function as a negative electrode
  • the protrusion region of 10 mm ⁇ 10 mm is a region that connects with the tab lead 2 c .
  • the negative electrode mixture layer 2 a formed on the above-described connecting region was scraped to expose the negative electrode current collector 2 b .
  • FIG. 3 ( b ) the negative electrode mixture layer 2 a formed on the above-described connecting region was scraped to expose the negative electrode current collector 2 b .
  • the exposed part of the negative electrode current collector 2 b was connected to the negative electrode tab lead 2 c and a predetermined region of the outer periphery of the negative electrode tab lead 2 c was covered with an insulating tab film 6 .
  • a counter electrode was produced by attaching a lithium metal foil to one surface of an electrolytic copper foil (current collector).
  • the counter electrode was cut out into the same shape as the negative electrode, and the lithium metal foil formed on the connecting region formed in the same manner as the negative electrode was peeled off to expose the current collector.
  • the exposed part of the current collector was connected to the tab lead in the same manner as the negative electrode, and afterwards, a predetermined region of the outer periphery of the tab lead was covered with an insulating tab film.
  • a nonaqueous electrolyte was prepared by dissolving LiPF 6 in a solvent mixture of fluoroethylene carbonate (FEC) and dimethyl carbonate (DMC) (volume ratio 20:80) at a concentration of 1 moL/L.
  • FEC fluoroethylene carbonate
  • DMC dimethyl carbonate
  • EBTMOS 1,2-bis(trimethoxysilyl)ethane
  • a cell with a designed capacity of 114 mAh, which is regulated by the negative electrode was produced.
  • the negative electrode and counter electrode were allowed to face each other with two sheets of a polyethylene made separator (thickness 15 ⁇ m) having an aramid coating so that the negative electrode mixture layer overlaps with the lithium metal foil, thereby producing an electrode group.
  • an Al laminate film (thickness 100 ⁇ m) cut into a rectangular shape was folded in half, and longitudinal ends were heat-sealed at 230° C. to form an envelope.
  • the fabricated electrode group was put into the envelope from one of short sides, and heat-sealing at 230° C.
  • the evaluation cell was sandwiched with a clamp between a pair of 10 ⁇ 5 cm stainless steel (thickness 6 mm) plates and fixed under pressure with 3.2 MPa.
  • the negative electrode In a thermostatic chamber at 25° C., the negative electrode was charged with lithium over 2 hours at a constant current of 0.05 C (1 C is a current value at which designed capacity is discharged by an hour), and the negative electrode was allowed to stand for 12 hours. The negative electrode was then charged further to a cell voltage of 0.01 V with a constant current of 0.05 C, and allowed to stand for 20 minutes. Lithium was then discharged from the negative electrode to a cell voltage of 1.5 V at a constant current of 0.05 C, and the cell was allowed to stand for 20 minutes.
  • the negative electrode was then charged with lithium to a cell voltage of 0.01 V with a constant current of 0.05 C, and allowed to stand for 20 minutes. Lithium was then discharged from the negative electrode to a cell voltage of 1.5 V at a constant current of 0.05 C and the cell was allowed to stand for 20 minutes.
  • the negative electrode was charged with lithium at a constant current of 0.3 C to a cell voltage of 0.01 V, and allowed to stand for 20 minutes, and thereafter, lithium was discharged from the negative electrode to a cell voltage of 1.5 V at a constant current of 0.3 C, and the cell was allowed to stand for 20 minutes: this cycle was repeated.
  • the ratio of the capacity obtained by the lithium discharge of the 50th cycle to the capacity obtained by the lithium discharge of 1st cycle was determined as 50th cycle capacity retention rate.
  • Table 1 shows the results.
  • Evaluation cells A2 to A7 were prepared and evaluated in the same manner as in Example 1, except that in preparation of the nonaqueous electrolyte, the content of EBTMOS to be added to the nonaqueous electrolyte was changed as shown in Table 1.
  • Evaluation cells A8 to A10 were prepared and evaluated in the same manner as in Example 1, except that 1,6-bis(trimethoxysilyl)hexane (HBTMOS) represented by the formula (1-2) below was added in an amount shown in Table 1 to the nonaqueous electrolyte instead of EBTMOS in preparation of the nonaqueous electrolyte.
  • HBTMOS 1,6-bis(trimethoxysilyl)hexane
  • Evaluation cells B1 and B2 were prepared and evaluated in the same manner as in Example 1, except that vinyltris(2-methoxyethoxy)silane (VTMS) represented by the formula (2) below was added in an amount shown in Table 1 to the nonaqueous electrolyte instead of EBTMOS in preparation of the nonaqueous electrolyte.
  • VTMS is the additive used in Non-Patent Literature 1.
  • An evaluation cell B3 was prepared and evaluated in the same manner as in Example 1, except that in preparation of the nonaqueous electrolyte, EBTMOS was not added.
  • FIG. 4 shows the relation between the charge/discharge cycle numbers and capacity retention rate of the evaluation cells A6, A9, B1, B2, and B3.
  • Table 1 and FIG. 4 show that the capacity retention rate is improved when EBTMOS and HBTMOS, which are the alkoxysilyl compound represented by the formula (1), are added to the nonaqueous electrolyte.
  • EBTMOS and HBTMOS which are the alkoxysilyl compound represented by the formula (1).
  • the effect of EBTMOS is significant, and the effect becomes remarkable according to the amount of the EBTMOS contained.
  • the effects of EBTMOS are generally saturated at the content of 4 to 5 mass % in the nonaqueous electrolyte.
  • Non-Patent Literature 1 cannot improve the capacity retention rate.
  • the additive for a nonaqueous electrolyte according to the present disclosure is suitably used for a nonaqueous electrolyte secondary battery in which a negative electrode active material contains a material containing a silicon element.

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